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Abstract Charge‐transfer excited state (CTES) defines the ability to split photon energy into work producing redox equivalents suitable for photocatalysis. Here, we report inter‐net CTES formation within a two‐fold catenated crystalline metal–organic framework (MOF), constructed with two linkers, N,N′‐di(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxydiimide (DPNDI) and 2,6‐dicarboxynaphthalene (NDC). The structural flexibility puts two complementary linkers from two nets in a proximal position to interact strongly. Supported by the electrochemical and steady‐state electronic spectroscopic data, this ground‐state interaction facilitates forming CTES that can be populated by direct excitation. We map the dynamics of the CTES which persists over a few nanoseconds and highlight the utilities of such relatively long‐lived CTES as enhanced conductivity of the MOF under light over that measured in dark and as a proof‐of‐the‐principle test, photo‐reduction of methyl viologen under white light.